The present invention relates generally to biologically active hydroximidates, thiolhydroximidates, amidoximes and, more particularly, to novel pesticidally active carbamate and sulfenylated carbamate derivatives thereof.
Carbamate derivatives of hydroximidates and thiolhydroximidates have heretofore been previously described. For example, U.S. Pat. No. 3,576,834 discloses acyclic compounds of the structure ##STR2## wherein Q is sulfur or oxygen and the insecticidal and acaricidal activity thereof.
Similarly, carbamates of monocyclic thiolhydroximidates of the structure ##STR3## are disclosed in U.S. Pat. No. 3,317,562 as insecticides.
Carbamate derivatives of bicyclic oximes have been previously reported. U.S. Pat. No. 3,231,599 discloses compounds of the structure ##STR4## as insecticidally active compounds.
Further, Belgian Pat. No. 766109 quinuclidine oxime carbamates of the structure ##STR5## also with reported insecticidal activity.
U.S. Pat. Nos. 3,317,562 and 3,574,233 further disclose thiabicycloalkanes and -alkenes of the formulas ##STR6## The patentees indicate that compounds of the above formulas possess insecticidal, fungicidal, nematicidal, antibacterial and herbicidal activity. It will be appreciated that the foregoing thiabicycloalkanes and alkenes are not carbamates.
U.S. Pat. No. 4,219,658 discloses lactones and thiolactones of the formulas ##STR7## as intermediates in the preparation of hydrocarbylthiomethyl-2,2-dimethylcyclopropane carboxylic acids useful as pesticides.
It has now been surprisingly found, in accordance with the present invention, that substituted heterobicyclic compounds of the formula (I) ##STR8## as defined hereinafter possess a broad range of useful biological properties, as well as a high degree of activity as arthropodicides, i.e., insecticides, acaricides, aphicides, etc., as well as nematicides.
As detailed hereinbelow, the compounds of the above formula (I) are chemically and biologically distinguishable from the acyclic and monocyclic hydroximidates and thiolhydroximidates, bicyclic oximes and thiabicyclo-alkanes and -alkenes described above in reference to heretofore suggested compounds by reason of the mode of action, type of action and level of action demonstrated for the compounds of the present invention, as well as the fact that the compounds of the present invention are not obtainable by previously suggested synthesis methods employed to prepare the prior art compounds which appear to be structurally similar.
Certain of the compounds of the present invention are derived from Diels-Alder adducts of thiocarbonyl compounds with cyclic dienes. the ability of carbon-sulfur double bonds to serve as dienophiles in the Diels-Alder reaction was first reported in 1965 by Middleton [J. Org. Chem. 30, 1390 (1965)]who described the reactions of perfluorinated thioketones, thiophosgene and thiocarbonyl fluoride with several dienes, including cyclopentadiene, e.g., ##STR9##
Since that time, many other examples of such reactions have been reported, including in addition to the above dienophiles such thiocarbonyl compounds as NCC(.dbd.S)SCH.sub.3 [Can. J. Chem. 49, 3755 (1971)], NCC(.dbd.S)NR.sub.1 R.sub.2 [Tetrahedron Letters, 2139 (1977)]RSO.sub.2 C(.dbd.S)SR' [Tetrahedron 30, 2735 (1974)], and ##STR10##
A limited number of reports have appeared on further reactions of the initial Diels-Alder adducts. Johnson et al. [J. Org. Chem. 34, 860 (1969)]describe oxygenation of the sulfur, followed by epoxidation of the double bond as depicted below: ##STR11##
The authors indicate that one chlorine can be reduced from the dichloro sulfone by treatment with divalent chromium: ##STR12## Reduction with lithium aluminum hydride yields the bicyclic thioalkene: ##STR13##
In 1973, Reich et al. [J. Org. Chem. 38, 2637 (1973)] reported the reaction of thiophosgene with cyclohexadienes, to yield 3,3-dichloro-2-thiabicyclo[2.2.2]oct-5-enes, as well as the hydrolysis of these Diels-alder adducts to the corresponding thiolactones. ##STR14## Benassi et al. [Synthesis 735 (1974)] describe a similar hydrolysis in the [2.2.1] system during reduction using an aqueous workup procedure: ##STR15## Raasch [J. Org. Chem. 40, 161 (1975)] reports on the addition of halogen or sulfenyl halides to the carbon-carbon double bond of the 2-thiabicyclo[2.2.1]hept-5-enes with rearrangement to yield the 6,7-disubstituted thiabicyclo[2.2.1]-heptanes, e.g., ##STR16## In 1976, Allgeier et al. [Tetrahedron Letters, 215 (1976)] also described the reaction of thiophosgene with anthracene to give the Diels-Alder adduct which is subsequently hydrolyzed to the thiolactone. Hong [Dissertation Abstracts International 40, 5672-B (1980)] states that solvolysis with methanol of the Diels-Alder adduct from thiophosgene and cyclopentadiene results in ring opening to yield (XIV) in almost quantitative yield. ##STR17##
For purposes of indexing, Chemical Abstracts classifies compounds of type X above as 2-thiabicyclo[2.2.2]oct-5-en-3-ones. In referring to these compounds, it is important to distinguish nomenclature used for indexing convenience from nomenclature signifying chemical type. Thus, Chemical Abstracts refers to both compounds XV and XVI (shown below) as thiabicycloalkanones. Chemically, however, compound XV is a thiolactone, i.e., a cyclic thiolester; whereas compound XVI [J. Org. Chem. 43, 4013 (1978)] is a true ketone and specifically a .beta.-thioketone. ##STR18## Esters and ketones are distinct chemical classes with many distinctly different properties. One of these distinctions is their reactivity with hydroxylamine. Ketones are known to react readily with hydroxylamine to form oximes: ##STR19## Esters or thiolesters (and their cyclic counterparts, lactones and thiolactones) do not react with hydroxylamine to yield the analogous hydroximidates or thiolhydroximidates. ##STR20## Instead they react with cleavage of the carbon-oxygen or carbon-sulfur single bond to yield as displacement products, the hydroxamic acid or, in the case of the lactones and thiolactones, a lactam (Advanced Organic Chemistry, Second Edition, Jerry March, McGraw-Hill Book Company, New York, 1977, p. 386, 388). ##STR21##
An example of the failure of thiolactones to react with hydroxylamine to yield thiolhydroximidates is reported by Bruice and Fedor [J. Am. Chem. Soc. 86, 4886 (1964)]. The authors confirm that thiolactones, e.g., thiolbutyrolactone, undergo hydroxylaminolysis in a manner analogous to their thiolester acyclic counterparts.
The hydroximidates and thiolhydroximidates, i.e., ##STR22## have been reported in the literature. At least four methods of preparation have been described. U.S. Pat. No. 3,576,834 (and the references therein) describes two of these: (1) the reaction of an iminoether hydrochloride with hydroxylamine and (2) chlorination of an aldoxime to form a hydroxamoyl chloride followed by reaction of the latter with a salt of a mercaptan: ##STR23## U.S. Pat. No. 3,787,470 reports the formation of thiolhydroxamate esters from nitroalkanes and alkyl mercaptans: ##STR24## Faust et al. [Journal fuer Praktische Chemie, Leipzig, 311(1), 61, (1969)] describe the conversion of a thiopyranthione to a cyclic thiolhydroximidate. ##STR25##
It will be seen from the foregoing that applicants have discovered that the Diels-Alder adducts of certain thiocarbonyl compounds with cyclic dienes are converted easily and in high yield to bicyclic thiolhydroximidates which not only possess significant biological activity but which are valuable as intermediates in the synthesis of carbamate and sulfenylated carbamate final products. Moreover, the outstanding arthropodicidal and nematicidal activity exhibited by these compounds is entirely unexpected in light of the prior art set forth hereinabove which relates to the ease of hydrolysis of the thiophosgene adducts, along with the reported inability of the thiolactones thus formed to react with hydroxylamine to yield compounds of the subject invention.
In addition to the above observations relative to the absence of prior art synthesis methods which would allow one to predictably obtain the compounds of the present invention by analogy, it is likewise important to note the material differences in biological activity observed with the compounds of the present invention compared to that of the seemingly related prior art compounds described hereinabove. In making such comparisons, it is again important to distinguish between nomenclature used for indexing convenience and nomenclature signifying actual chemical type. For example, for indexing purposes, Chemical Abstracts would describe the compounds of the present invention, as well as those of formulas (XXI)-(XXIII) as carbamates of bicycloalkanone oximes. However, in reality, the compounds of formulas (XXI)-(XXIII) are derivatives of true oximes; whereas, the compounds of the present invention are derivatives of hydroximidates or thiolhydroximidates. The significance of the foregoing distinction is readily apparent when one considers the work of Huhtanen and Dorough [Pesticide Biochemistry and Physiology 6, 571 (1976)] who have shown that the chemical difference between the ketoxime derivative XXIV and the thiolhydroximidate derivative XXV ##STR26## results in surprisingly marked differences in their biological activity. Although both (XXIV) and (XXV) are insecticides, their spectrum of activity, persistence, use pattern and method of application are totally different. It is evident that these documented differences result from the difference in chemical structure between a true ketoxime and a thiolhydroximidate. It will also be appreciated that a similar distinction between the compounds of the present invention and compounds of formulas (XXI)-(XXIII) prevails.